Process for the production of nitric acid



Jan. 2, 1940.

7 Scrub be,"

H. A. BEEKHUIS, JR

PROCESS FOR THE PRODUCTION 0F NITRIC ACID Original Filed Nov. 9, 1933 s sant-sheet 1 ATTORNEY Jaw 2, 1940 H. A. BEEKHUls, JR 2,185,579

PROCESS FOR THE PRODUCTION OF NITRIC ACID original Filed Nov. 9, 1953 5 shntssheet 2 ATTORNEY Pate'ntea Jan. 2'1940 f 2,155,579 l PRooEss rolt' THE PRODUCTION "f lHerma A. B eeklfn1is.lr.,y Petersburg, Va., as#

.joF 7 signor, by mesne assignments, kto The Solvayr ProcessCompanyyNew York,fN. Y.,` a corporation of New York l Application November 9, 1033, Serial No. 697,240 Renewed October 27, 1938 I'Il'his invention relates" to a process lfort-he production of nitric acidfrom nitrogen peroxide vand With'thewater toforninitricacid.v The reaction particularlyvto a process vfor thel production ofa relatively'concentrated nitric; acid `by absorption of-v nitrogen acid. j f

Numerous processes have heretofore been pro.-

Aposcdmfor the absorptionv of nitrogenoxides, particularly'nitrogen'I peroxide (NO2) in Water to form nitric acid. The reaction taking place may beexpressed by the equation:

cNog+H2O=No+2HNo3f (NO) to nitrogen peroxide which may then react` may then be expressed by the equation: 'I II zNoz-qfngoa-osogznnog Water to form a ydilute aqueous nitric acid, -the above reactionirsan equilibrium reaction; that'is tofsay, nitricacidand nitric ,oxide tend to. react toformwater and nitrogen peroxide. For a given l concentration of nitrogen peroxide and of aqueous nitricl acidincontact with each-,other there is a definite partial ypressure of vnitric oxide. A dem4 crease in the concentration of nitrogen peroxide or an increase in the concentration of the nitric acid favor the reaction'of then'itric` acid and.l

nitricoxide. to form waterand. nitrogen peroxide. Thus, forlany given concentration of nitrogen peroxide in lthe gascontacted ivithwater orl dilute nitric acid there is adefinit e limitation to the concentration ,offnitric 4acid which may `befornied due toy the increasing concentration ofthe `nitric oxide formed bythe-reaction of nitrogen peroxide vand water. With oxygen present therea'ction'of y theg-nitric oxide to form nitrogen peroxide is` moderately rapid so long as the concentration of the nitric oxide correspondsto about 0.1 toyl at" mosphere partial pressure of NO. Forv low lconf` centrations oi nitrcoxide, for'example with nitric oxide ,partial vpressures below about 0.01 yatmosphere, its reactionwith oxygen is slow. Althoughr no special difficulty is involvedin obtaining nitric acidup tor 6,0%? to 70% strength from nitrogen peroxide andoxygen', sincethis involves partial.

` pressures of NOfin equilibrium :with the nitric acid ofabove about 0.01 atmosphererwhen it is 'attempted-togproduce directly an vacid of greater strength, special rneansmust be used to` increase i the otherwise very low rate of reaction between the nitricpxideandoxygendue tolthelow nitric. oxid,` concentration in equilibrium With therelatively vhighly concentrated nitric acid.

Itis arr- ;vob'ecmtherefore,',of this inventicnlto` providerA process. whereby the reaction 0f` nitrogen peroxide .f with water to form nitric acidv may be l oxidesfinvwater orina dilute nitric i orwhenfoxygenis' present in the nitrogen peroxide III @gas this 'oxygengserves toy re-oxidize nitric oxide- While nitrogenv peroxide "reacts vreadily with.

promoted and the reverse reaction of nitric acid` with nitric oxide may. be inhibited. Thus the di-l rect production 0I" relatively concentrated'nitric acid by absorption of nitrogen peroxide inwat'er or dilute nitric acid may be facilitated.

I have discovered that when nitrogen peroxide is absorbed in nitric acid solution in the presence of chlorine4 that nitrosyl chloride is lformed. In jthe presence of yrelatively concentrated nitric acid solutionfthe nitrosyl chloride is evolved from the solution substantially free from nitric oxide.

This reaction may be expressed by the equation:`

3No2+0.5C12+H2o=2r1No+Noc1 That this reaction Will take place and -nitrosyl` Achloridebe evolved from the concentrated nitric ciently rapidly `to oxidize the nitric 4oxide to nitrosyl chloride and thus--inhibitthe vreaction of the nitric oxide Withy the nitric acid..

As noted above,l the oxidation oinitric oxidein concentrations corresponding to partial pressures of NO below about 0.01 atmosphere is so slow as to bea serious handicap in the production of concentrated nitric acid by the directabsorption of nitrogen peroxide in Water or in dilute nitric acid. However, with. chlorine present it is `feasible to operate under lconditions which correspond to a nitric oxide concentration equivalent to a partial `pressure of NO 0150.0003` atmosphere or `even less,l

and a concentrated nitric acid may readily be produced Aby the direct absorption of nitrogen peroxidein the presence of chlorine. The nitric acid thus obtained by absorption of nitrogen peroxide from a gas containing chlorinecontains chlorine (either free .or combined) which may, however, be readily stripped from the concentratednitric yacid by heating the acid, preferably While passing av gassuch as oxyge'nginflcontact with the heated acid; Nitrosyl chloride and some nitrogen peroxide gas may thus be evolved from the nitric acid and'a pure concentrated nitric acid obtained.

`In carrying out the process of this invention for theproduction of nitric acid, nitrogen peroxide is treatedqwith an. aqueous liquor such as water or dilute nitric acid in the presence of chlorine and the resulting. aqueous nitric acid` solutionL which duringthe absorption of the nitrogen peroxide is at ordinary atmospheric rtemperatures may then nitrosyl chloride to nitrogen peroxide'and chlo- 1 air.

be heated, for example, to a temperature above about 50 C., to free it of chlorine,` particularly combined chlorine.

In carrying out a process for producing nitric' acid by reaction of nitrogen peroxide With-water, 4 .y y

may/contain upwardly of 95% to 100% HNO3.1 `An embodimentof this aspect'of the invention the aqueous liquor used for treating the nitrogen peroxide may originally contain nitric acid in amount corresponding to above about 40% HNO3 or if a more dilute acid or water is employedin the course of absorbing and reacting the nitrogen peroxide with water, a nitric acid of this concentration (above about 40% I-INOs)V may be formed. The process of this inventioni'comprises the treatment of an aqueous nitric acid contain-` ing above about 40% HNO3, such as the acids referred to, with nitrogen peroxide and chlorine,A

the chlorine being present vin amount sufficient to maintain the partial pressure of nitric oxide below about 0.01 atmosphere during the reaction of the nitrogen peroxide with thenitric acid@k The process of this invention furtherl comprises the treatment of nitrogen peroxide with both an aqueousV liquor and oxygen inthe presence of chlorine, the oxygen being employed in the proportions oi about 0.5v mol or more of oxygen for every 2 mols of NO2 andl the chlorine being preferably present in the proportionsfof about 0.5 mol C12 or more for,` every 3 mols of, NO2.

A preferred embodiment of the invention comprises passing a gas containing nitrogen peroxide and chlorine in contact with a dilute aqueous nitricacid containing, for example, below about 70% HNOs, and preferably about 40% to'70% HNOS, to form a more concentrated aqueous nitric acid, preferably one containing more than 70% HNOa, by absorption of nitrogen peroxide. The chlorine is preferably employed in the proportions of about 0.5 mol or more of chlorine for every 3 mols of nitrogen peroxide. The resulting concentrated nitric 'acid solution may then be heated to free it of chlorine, preferably while passing oxygen in contact with the heated solution either'as a concentrated oxygen gasor as The gases evolved in this treatment o`fthe heated nitric acid may be introduced into the nitrogen peroxide gas passed 'in' contact with the dilute nitric acid. The gases passing v out of contact with the nitric acid, which contain' nitrosyl chloride,v may be treated'to oxidizethe rine, and this chlorine-containing gas returned for reaction with additional nitrogen peroxide, water and nitric acid to form concentrated nitric acid.

production of highly concentrated nitric v`acid containing, for example, 95% up to 100% HNOS. As noted above aqueous nitric acid containing up to about 70% HNOs may be prepared by the absorption of nitrogen peroxide in water, but to make acids of higher strength requires special provisions to increase the rate of oxidation of the nitric oxide. Nor may the aqueous acids of 70% HNOa or below be distilled to produce a highly concentrated acid. `Nitric acid '(HNOaland water form a constant boiling mixture con-l taining about 68% HNO3 so Lthat no Iacid otl a higher concentration than 68% may be obtained by distilling a weaker acid, nor-is it practicable to obtain a concentrated acid by? distillingone containing but little more than 68% HNOa, such as an acid containing about 707% HNOL This invention, however, comprisesla process wherein a nitric acid containing above 70% "HNOz is distilled to yield'a'dilute nitricracidresidueand raqueous nitric acid containing, say, 68% to 751%1 HNOY inv the presence of chlorine untillthe acid j `contains about to 90% `I-INOs. This more ing, forv example, about 68% to 74% HNOais inthrough at a temperature of, for example, about' lide and chlorine, particularly chlorine combined* This invention is of particular value in the.

passedupwardly in Contact with the descending? .contain nitrogen peroxide, chlorine-,nitrosyl chloe" .-'f'

. remove from the acid at ordinary'at'miospheric formed by reaction of nitrlog'enjgperoxidewith water or a dilutevaqueous vnitric acid,-f-a'ndthis relatively concentrated acid is -thensfractionally a-highlyconcentrated nitric acid product; which comprises reacting nitrogen. peroxidewith an 1 concentrated acid may then be fractionally disftilled'to obtain a relatively dilute nitricacid as a `residue and a concentrated -nitric acidfcontaining about or up `to 100% HNO3 as ahlA distillate. l "f1 For a further understanding kofthis inven on reference vis had to the -foll'o'wingdetail'edd scription of processes for the lproductionfof'a" concentrated nitric acidfrom water or r'e1at-i-ijelyfjV dilute nitric acid which are illustrated in` -f accompanying drawings. Inthe drawings Fig. 1 shows a process for the reaction'fof gen peroxide, oxygen .andV water-toformcentrated nitric acid.

Fig. 2 illustrates the use-of the process offth'i's invention in conjunctionwith the treatment of "a liquid mixture of nitrosyl chloride andchlotroduced. A mixture of nitrogen peroxideaV chlorine is introduced into the bottom of towery I and is passed-upwardly vthrough the'towerfin" contact with the nitricacid descendinggthere-l 30 C. There iiowsoff 'from thebottorn' of Athe' tower a relatively'concentrated aqueousnitric-acid solution 'containing-some dissolvedv nitrogen perox-;

nitrosyl chloride. vThe nitric acid may alsoco tain chlorine in combination as hydrochloric acid; This acidy solutionis introducedginto the top, of tower 2 which operates as .'idesorben` 4'Tower-'Tis provided with 'a heater tol heatthe nitric 'acid de` scending through the tower to a temperature within the range of 50 'to 100 "C." Oxyge also introduced' into the bottom of the tower'farid ride and oxygen. Instead of heating thefnitricacid in--jdfesorb`er" 2 and treating it at 'anelevated' temperature* with a relativelyrsrnalll amountjof oxygengast/'asdescribed above, the acid fromv absorption 'tower I may be treated in 'desorber 27byvmeans of "ai'rj or other gas vinert towards nitric acid'pa'ssed'f through the 'describen in'arnount-sufcient to temperatures nitrogen peroxide, I' nitrsyl" 'chlofaJ 1 ride and chlorine contained therein. In thus treating the acidthe gas leaving the desorber will contain -relatively small proportions of nitrogen peroxide, nitrosyl chloride and chlorine 5 whichvmay be recovered,- if desired, by absorption in water' or the gas leaving the desorber may be discharged rwithout further treatment.

The relatively dilute nitric acid introducedV into absorption tower I is treated with the gases containing nitrogen peroxide and chlorine in such amount that the nitric acid solution after treatment in desorber 2 contains from 80% to 90% LI-INOs. This relatively concentrated nitricacid `is lintroduced into the mid-portion ofA a towerl 3, t the bottom of vwhich is provided with a heater. In this tower the entering nitric acid is passed downwardly in contact with relatively dilute nitric acid vapors to evolve nitric acid andwater y vaporsfrom the entering nitric acid and the :o mixture of nitric acid and steam vapors pass upwardly through the tower in contact with reiluxed nitric acid, and thence to a condenser 4 where they are condensed to form nitricfacid. `A portion of this condensate is returned to the top B5 of tower 3 as a nitric acid reilux. The amount of reflux is so regulated that upon 'condensing the nitric acid vapors leaving the top of the tower, al nitric acid of about 95% to 100% HNOa is formed. This relatively concentrated nitric acid, as noted above, is in part returned as reflux to the topv of tower 3 and the remainder is withdrawn as a concentrated nitric acid product of `water vapors for treatment of the more con'- centrated acid introduced into the mid-portion of thisl tower from desorber 2. Suflicient vapors are evolved from this nitric acid in the bottom of tower 3 so that it contains `froml 68% fto 74% HNOi,A which is withdrawn from the bottom of the tower and is returned to the `upper portion of absorption tower I for treatment with the gas v containing nitrogen peroxide and chlorine.

Il The gasesy from the top of absorption tower I contain nitrogen peroxide and nitrosyl chloride together with some chlorine and oxygen. These gases `are passed through a 'heat yexchanger 5 and 4thence to an oxidation chamber 6, where I0 nitrosyl chloride is oxidized to nitrogen peroxide and chlorine by means of the oxygen contained in-the gas. The hot gaseous products `of this oxidation treatment pass through heat exchanger 5 serving to preheat the incoming gas containing Il nitrosyl chloride and are then introduced into the nitrogen peroxide gas on its way to absorpfv A portion of thegases from the top of absorption tower I are continuously with-v l tion tower I.

4drawn to a scrubber 1 where they are washed with water to absorb the nitrogen peroxide, ni-

trosyl chloride and chlorine, aswell as lany nitric acid which may be present in this withdrawn gas. from the top of scrubber 'I while the dilute aquebl ous solution from the bottom of scrubber 1 is introduced into the top vof absorption tower If.

and illustrated in the drawings the proportions gas introduced into the bottom of absorption tower AI are such as to form the desired relatively leaving tower I and the 95%' to `100% acid from The unabsorbed inert gases are vented` In carrying out the process described abovev of water introduced into scrubber I'and thence; V0 into vabsorption tower I and of nitrogen peroxide.

concentrated nitric acidyof 80% to 90% HNOa) Il; tower 3.v Since theoretically all of the' chlorine gas present in the'nitrogen peroxide gas introduced into the bottom of absorption tower I' may be recovered as-nitrosyl chloride, which may beoxidized tov nitrogen peroxide and chlorine and reintroduced into absorption tower I, once the .lcdesired' proportion of chlorine has been intro' duced into the cyclic systemin which the procedure described above is carried out, no` further addition of chlorineis requiredexcept that necessary to make up for the chlorine losses from the system, for example, that lost with the inert gas withdrawn from scrubber I or the unavoidable losses .of rmaterials always encountered in the actual carrying` out of chemical processes. The Oxygen'required for reaction of the nitrogen 1Q g peroxide With the vwater is introduced into the bottom .ofy desorber Zand thence passes to absorptiontower I. -In the continuous operation of I the process described above the nitrogen peroxide and oxygen are introduced into the system in mi;

thel proportions of'about 4 mols of nitrogen` peroxide for each l mol of oxygen`together with the required amountof make-upl chlorine, As illustrative of the approximate composition of the gases inthe process described above, it may 2Q:

be said thatthe gas leaving absorption tower I passing to heat lexchangerv 5 may contain about 0.5 mol of NO2 to 1.5 mol NOCI to 0.5 mol C12 to 1 mol O2.` The gas after oxidation of nitrosyl in oxidation chamber 6 may contain 1.5 mols 31h;4

NO2 to 0.5 mol NOC] to 1 mol C12 to 0.5 mo-l O2; To this gasv there is added about 2 mols of NO2 for every 1.5 mols of NO2 inthe gas from the oxidation chamber 6, and about 0.5 mol oxygenl are introduced into the bottom of desorber 2 for 85revery 2 mols of -NOzfintroduced into the gas leaving oxidation chamber 6. If desired, the distillation and rectification of nitric acid in tower 3 may becarried out under a reduced pres sure below atmospheric. The acid from desorber 40 2 may also, if desired, be treated with concentrated sulfuric acid to obtain a more concentrated nitric acid (95% to 100% HNOg) instead of being subjected yto the distillation treatment described above. It

Referring now to'Fig. 2, the numeral 8 indicates a fractionating column in which-a liquid mixture of nitrosyl chloride and chlorine which is Vaporsof nitrosyl chloride' are continuously 50" withdrawn from thebottom portion of column 8, are mixed with oxygen gas sulicent for the oxidation of nitrosyl chloride to chlorine and nitrogen peroxide, and are passed through a heat exchanger II and thence to an oxidation chamber M I2.l The hot products of reaction from oxidationv chamber I2 pass through heat exchanger I I in heat exchange relationship with the incoming nitrosyl chloridev gas and serve to preheat this gas to a temperature at which the reaction of the 70.; oxygen and nitrosyl chloride is initiated.' This reaction is exothermic so that in passing through' oxidation chamber I2 the temperature of the re should not be permitted to 'rise above abouty 400i C. AThe reactionfproducts from heat exchanger il, are passed in series first through a cooler I3;

which was unoxidized in the'passage ofthe gasesv k-1. through oxidation chamber. l2. In cooler I4 the gases from cooler i3 are` further cooled to condense out a desired proportion of the chlorine. This liquid chlorine, which may also contain.

some nitrosyl chloride and nitrogen peroxide, is lvintroduced into the mid-portion of column 8 for the separation of the chlorine Yfrom the nitrosyl chloride and nitrogen peroxide, the nitrogen per-`` oxide becoming mixed with the vapors oi=nitrosyl chloride withdrawn from the bottom of column 8. The cooling of the gases in.` cooler It is carried tosuch a degree that the chlorine Content of the gases leaving this cooler, together with the chlorine in the liquid nitrogen' peroxide removed from cooler I3, amounts to about 0.5 mol of chlorine 2li-rior every 3 mols of NO2 in the liquid and gas containing this chlorine. This liquidi and gas are both introduced into the bottom portion of an absorption tower It .containing bubbling plates or a packing for promoting intimate contact beaoitween an aqueous nitric acidintroduced into the top of the tower and passed downwardly in cointact with the ascending gases comprising chlorine and nitrogen peroxide. If desired, the `liquid. nitrogen peroxide in cooler I3 may be vaporized si'ibefore being introduced into't'ower i5 or, if thek nitrogen peroxide ispassed directly as a liquid into this tower, it will become vaporized by the absorption of heat from the acid with whichit is contacted in the tower. The nitrogen peroxide and chlorine react with the nitric acid in tower o I5. in the manner described above in connection with the operation of absorption ytower I of Fig. 1 of the drawings, and the resulting relatively concentrated nitric acid is'withdrawn from theA bottom of tower I5 and introduced into the top' of a. desorberiii where it is heated andy treated with oxygen gas as described above in connection with the operation of desorber 2of Fig. l. The concentrated nitric acid is withdrawn from the bottom ofdesorber it. The gas containing ";nitrosyl chloride, oxygen and some chlorine from the top of absorber I5 is introduced vinto the nitrosyl chloride gas passing fromy rectification column B to heat exchanger lI. The oxygen re- ;quired for loxidation of the nitrosylchloride in "oxidation chamber l2 is introducedinto the bottom of desorber i5.

It may be noted that in carrying out the process of Fig` 2 as described, the chlorine content of the nitrosyl chloride withdrawn from the bottom of 00""rectication column 8 is all removed as liquid chlorine from cooler it and recovered as a rela tively pure liquid chlorine from cooler 9. There is maintained, however, in the gas cyclic system,

gli desired, both absorption tower I5 and desorber oxide, chlorine and somev residualv nitrosyl. chlor of absorption tower24 and passedinto the top of'" i6 may also be operated under a pressure in ex.-v cess of atmospheric, although it is preferredl to y employ substantially atmospheric pressure in `lie-5. sorber It evenl though a higher pressure lbe main- A tained in absorptiontower I5. l f; With reference tothe process llustratedinFigsi 3, a gaseous mixture of nitrosyl Achloride fand chlorine may be compressedl in the compressor; -I to, for example, Batmcspheres and passed into aA cooling coil I'whereit is cooled toga temperature 1G oi, for example, 1050. toliqueiy both the nitrosyl chloride and the chlorine. `The uncondensed:v inert gases pass out of the top of cooling coil-I3 while the liquid nitrosyl chloride and 1chlorin`e may be introducediby means ofapump lia-into; 15 the midportion of the reetication column 2li.;A In column 2U the liquid mixtureof nitrosylgchlo.-I Y ride and chlorine is fractionaliy distilled-to,.sepa- ;l rate the chlorine and nitrosyl chloride inpthe: manner described above in rconnection with thegg operation of column 8 of Flg. 2,'except thatthe. amount oi nitrosyl chloride vaporized in the'ibotfi; tom of column 2li is limited to thatsuflicient-ffor, the ldistillationy fromy the liquidmixture of jthe; chlorine and the remaining nitrosyl chloridey isl i;

Vwithdrawn as a liquid from the bottom of column El), and is passed `to a heater 2l toI vaporizethe',-f.V liquid; The vaporizedf nitrosyl chlorideis mixed', with suflicient oxygen for its oxidation togiorm nitrogen peroxide and chloriney and is then heated and passed through an: oxidation chamber- 122 at.- l a temperature of about 250 C. inl contactwith'. a catalystv promoting the oxidation of nitrosyll Chloride. y y y The gas leaving oxidationchamber 22 is cooled .3.5a .to a temperature at whichnitrlc oxidereacts, y preferentially with the free oxygenr contained in.y the gas instead of the free chlorine therein; for. example a temperatureoi about C. 'orbelovvtf and at this temperature is 'mixed with suiiicielitu nitric oxide to react with the oxygen inY the gas .4 to form nitrogen peroxide. The gases nia-yfbe@V passed through an. oxidation chamber Zligtogve` sumclent time for. the reaccionar the nitric oxide; with the oxygen and, if desired, this ,oxidation 5i chamber may contain a catalyst promotingthey Y' reaction. The gasnow containing nitrogenperride not oxidizedV in oxidation chamber 1.22 is.; i passed into the bottom of an absorptionftower 2,4,v Where it is passed in countercurrent. flow with.v aqueous nitric acid containingior example, about 75% HNOS which reintroduced into theftopo"f the tower. The nitrogenperoxide is absorbed .i y the nitricY acid and reacts with theWat-erfinthe presence oi chlorine to form a more concentrated nitric acid whichis withdrawirfrom thebottom.;

an. desorber 25. ,The residual unabsorbed gases:r leaving the top. of tower '24, containing nitrosyts chloride and chlorine may be ,returnedv to and 0u? mixed with the nitrosyl chloride-chlorine con-v n taining gas passing through compressorVA Il tofeooungeon sa .whereby the nitrosyl Chloride. and! chlorine content of the gases from tower 2,111 may4v be treated4 in the manne-r -describednabove, Vtoi-: M gether with this fresh nitrosyl chloride-chlorine gas. f w -In desorber 25. the nitric acid is heatedy to` ai temperature of, for example, 510 to 100?, C. 'A or'v'm higherto strip it of chlorine and any adsorbed f. nitrogen oxides, and a portion of the thustreatedr nitricacid is returned tothe topv ofibsorp',tion A towerZftvafter'being diluted with the-'requis e; amount of water to form a.so1ution:containing 'm about'75'% HNOS. Theremaining portior'i'of the .concentrated nitric acid 'from' desorberl may be'withdrawni as a product of thisprocess.

" 'Sincenumerous changes may be made. in the .particular processv described above ywithout de.- parting from the scope of `tl;1e-inventionthe exvample'given is tof-be understood as illustrative of the invention {rather than limiting it. In my copending applicationSerial No; 225,872,

filed August 2i), 1938, as acontinuation-in-part of this application, I am claiming the process for reacting nitrogen peroxide and chlorine to form 4 a nitric acid containing at least '70 parts HNO'a Vto 30 parts IfIzO disclosed herein. rI 'f f-Iclaim: v w11. In a process for the treatmentof nitrosyl chloride to Iobtain nitricacid andl chlorine from the nitrogen andchloriney combined therein, that limprovement which comprises introducing said nitrosyl chlorideinto a circulatory system vand yin'saidsystem oxidizing the nitrosyl chloride ,to

nitrogen peroxide and chlorine, reacting-the resulting nitrogen peroxide with an aqueous liquid and `chlorine at a temperaturey at ywhichgthefnitr'ogen peroxide is absorbed by said aqueous liquid and reacts withwater contained therein to form nitric acid and Anitric oxide and the nitric oxide reacts with the chlorine to `forni nitrosyl chloride, separating from the nitric acid the nitrosyl chloride formed by reaction of thechlorine and l'n'itric'oxide recycling the thus separated nitrosyl chloridein Athe aforesaid vcirculatory .system together with fresh nitrosyl crdoride introduced thereinto .and withdrawing lfrom said system excess 'chlorine liberated by the aforesaid oxidation of'nitrosylchloride. v

2.'In a. process'for the treatment of nitrosyl chloride to obtain nitric acid .andphlorine from the nitrogen and chlorinecombined therein, that improvement which,y comprises introducing said nitrosyl chloride into aycirculatory system and fin-said s'yst'emoxidizing the nitrosyl chloride to nitrogen'peroxide and chlorine, treating the resulting mixture of nitrogen peroxideand chlorine with an aqueous liquid ata temperature at which l the nitrogen peroxide is absorbed by said aqueous 'liquid and-reacts `with water contained therein to 'form nitric" acid and nitric oxide andthe nitric oxide reacts with .a part of said chlorine to form nitrosyl chloride, treating said mixture of nitroi gen lperoxide and chlorine with the aqueous liquid -in proportions such that gaseous nitrosyl 4chlo- `ride is evolved from the nitric-acid formed by reactionA of said aqueous liquid andnitrogen peroxide, separating from' the nitric,y acid the nitrosyl chloride formed by reaction of saidI chlorine l and nitric oxide, recycling thethus separated nitrosyl chloride in the 'aforesaid circulatory system together with fresh nitrosyl chloride introduced thereinto and withdrawing from said system excess chlorine liberated by the 4aforesaidoxidation of nitrosyl chloride.

3; In a process for the treatment oa mixture of `nitrosyl chloride and chlorine to obtain Vnitric acid from the nitrogen combined as nitrosyl v chloride and separately recover the chlorine, that improvement which. comprises introducing said 'l nitrosyl chloride and chlorine into a. circulatory .system andin said system liquefying saidnitrosyl v'chloride and chlorine, riractionally, distilling the` resulting liquid mixture to separate chlorine from the nitrosyl chloride, vwithdrawing the chlorine from 'said lcirculatory system, -oxidizing the nitrosyl chloride to form a mixture of nitrogen peroxide and chlorine, passing said'mixture'A of nitric acid and nitric oxide and the nitric oxide Y.reacts with a part of thechlorine to'form nitrosyl .nitrogen4 peroxide, and recycling the resulting ous liquor and reacting the nitrogen peroxide nitrogen yperoxide and chlorine in contact with an aqueous liquor at a temperature at which nitrogen peroxide is absorbed by said aqueous liquid and reacts with water contained therein to form l chloride, contacting said aqueous liquid, nitro-1 gen peroxide and chlorine in proportions such that gaseous nitrosyl chloride is evolved from the nitric acid formed by reaction of the'aqueous im :liquid and nitrogen peroxide, and recycling the "resulting'mixture of nitrosyl chloride and un- 'reacted` chlorine in said circulatory system tov'g'ether with fresh nitrosyl chloride-chlorine gas introduced thereinto. .l

. `i. In a .process for the treatment of a mixture of 'nitrosyl chloride and chlorine to obtain nitric acid from -the nitrogen combined as nitrosyl chloride and separately reco-ver the chlorine, that improvement which comprises introducing said f2() nitrosyl chloride and chlorine into a circulatory system and in said system liqueiyingsaid nitrosyl chloridey and chlorine, fractionallydistilling the resulting liquid mixturev to separate chlorine from the `nitrosyl chloride, withdrawing the chlorine 25 from said circulatory system, mixing the nitrosyl chloride with oxygen and heating the mixture to oxidize the nitrosyl chloride to nitrogen peroxide and chlorine, introducing into the reaction product thus obtained at a temperature of about a0 100 C; nitric oxide in amount suiicient toreact with residual free oxygen in said reaction productto form nitrogen peroxide, passing the gas containing nitrogen peroxide and chlorine thus obtained in contact with an aqueous'l liquor ata ,135 temperature at which nitro-genperoxid'e is ab-V sorbed by said aqueous liquid and reactsr with water contained rtherein to form'nitric acid and vnitric oxide and the nitric oxide reacts witha part of the chlorine to `forno nitrosyl chloride, contacting said aqueous liquid, nitrogen peroxide and chlorine in` proportions such that gaseous nitrosyl chloride is evolved from the nitric acid formed by reaction of the aqueous liquid and mixture of nitrosyl chloride and unreacted chlorine in said circulatory system together with fresh r'nitrosyl chloride-chlorine gas introduced thereinto.

5,. The process for the treatment of a gaseous mixture of nitrosyl chloride and chlorine which comprises cooling said mixture tofcondense a liquid mixture olf-,nitrosyl lchloride andchlorine,

`iractionally distilling said liquid mixture to sepand a part of the chlorine with the 'aqueous liquor with the 'formation' oi nitric acid and nitrosyl chloride, introducing nitrosyl chloride, thus formed and mixed with unreacted chlorine into the aioresaidgaseous mixture of nitrosyl Chlo-izo ride. and chlorine and treating the mixture thus obtained in the manner described to separately recover chlorine and nitrosyl chloride therefrom,

to oxidize the nitrosyl chloride and to react the u,

nitrogen peroxide thus .obtained with an aqueous liquid.

6; Inv a. process for the treatment of nitrosyl chloride to obtain nitric acid and chlorine from `the nitrogen and chlorine combined as nitrosyl.

chloride, that improvement which comprises introducing saidnitrosyl chloride into a circulatory system and in said system heating the nitrosyl chloride With oxygen to -oxidize it and to form a gas containing nitrogen peroxide, chlorine and free oxygen, introducing nitric oxide into said gas at atemperature at Which the nitric oxide reacts preferentially with the free oxygen instead of with the free chlorine in said gas, treating the resulting mixture of nitrogen peroxide and chlorine'With an aqueous liquid in the presence of Achlorine at ordinary atmospheric temperatures atv cycling the nitrosyl chloride formed by the re- 'action of the nitrogen peroxide, chlorine and aqueous liquid in the aforesaid circulatory system together with fresh nitrosyl chloride introduced thereinto and withdrawing from said system excess chlorine liberated by the aforesaid oxidation of nitrosyl chloride.

v'7. The process for the treatment of a liquid mixture ofA nitrosyl chloride and chlorine which lconil'cryis'es fractionally distilling said liquid to recover the chlorine separate from the nitrosyl chloride, oxidizing the thus separated nitrosyl chloride, cooling the gaseous mixture containing nitrogen peroxide and chlorine thus obtained tolliquefy nitrogen peroxide and leave chlorine as a gas, cooling the gas containing chlorine to liquefy chlorine therefrom, introducing the lique- `lied chlorine into the aforesaid mixture Vof nitrosyl chloride and chlorine being fractionally distilled, reacting the aforesaid liquefied nitrogen peroxide with `aqueous nitric. acid in the presence of chlorine with the formation of nitric acid and nitrosyl chloride, and mixing the nitrosyl chloride thus formed with the aforementioned nitrosyl chloride separatedfrom chlorine prior to the described oxidatio-n of the nitrosyl chloride.

`8. The process forthe treatment of a liquid mixture of nitrosyl chloride and chlorine which comprises fractionally distilling said liquid to recover the chlorine separated from the nitrosyl chloride, oxidizing the thus separated nitrosyl chloride, cooling the gaseous mixture containing `nitrogen peroxide and chlorine thus obtained to liquefy nitrogen peroxide and leave chlorine as agas, cooling the gas containing chlorine to liquefy chlorine therefrom, introducing the liquefied chlorine into the aforesaid mixture of nitrosyl lchloride and chlorine being fractionally distilled, reacting the aforesaid liquefied nitrogen peroxide With aqueous nitric yacid in the presence of chlorine with the formation of nitric acid and nitrosyl chloride, oxidizing nitrosyl chloride thus formedA to,` nitrogen peroxide `and chlorine, and treating the oxidation products .thus obtained together with the aforementioned gaseous mixture containing nitrogen peroxide and chlorine for condensation of liquid nitrogen 'peroxidezand of chlorine in the manner described.

9. The process for the production ofnitric acid which comprises reacting nitrogen peroxi'defwith an aqueous liquid in the presence of chlorine with the'formation of nitric acid and nitrosyl chloride, l-

oxidizingthe nitrosyl chloriderb'ymeans of oXy-A gen, to form nitrogeniperoxide and chlorinel and reacting the products of said oxidation together with additional nitrogen peroxidewith an aqueousliquid to form nitric acid. E 10. The process 'for the lproduction. of lnitric acid which comprises passing ana'queous liquid 'in contact with a ow of? gas containing nitro-` gen peroxide and chlorine and reacting nitrogen peroxide and chlorine in said gasy With the aqueous liquid with the formation of nitric acid andY nitrosyl chloride, heating the nitric acid thus.; formed .to free it of nitrogen oxidesl and chlorine,

introducing the thus liberated nitrogen oxides and chlorine (free and combined) -intothe aforeoxide andfchl'orine by heating the gases. Withizv oxygen and introducing .the products of said j said gas containing nitrogen peroxide' passe'drin oxidation into; the aforesaid nitrogen peroxide` gas passed in Contact with the` aqueous liquid.

11'l The process for 1-the production ofLv nitric acid from nitrosyl chloride .and nitric oxide WhichiI comprises' oxidizing said nitrosyl v'chloride 'by" f means of oxygen to vform a gas mixture containing nitrogen peroxide, chlorine'- and unreacted oxygen, thereafter introducing nitric oxideinto said gas mixture and preferentially reacting' said nitric oxide to produce nitrogen Yperoxide with. 'p

'the free oxygen instead of with the free chlorine in said gas mixture, reacting the nitrogenperoxide in the resulting gasv with an aqueous liquid and chlorine contained inthe gas at a tempera- .Q40 ture at which the nitrogen peroxide is` absorbed f Y by said aqueous .liquid Yand reacts. with` water contained therein to' form nitric acid andf nitric i oxide and-this nitric oxide reacts Withkthechlorine to rform nitrosyl chloride.

. .'45 12. The process for the production of nitric acida-nd chlorine from nitrosyl vchloride and nitric oxide which Acomprises introducing said nitrosylv chloride into a vcirculatory system and in said system oxidizing the nitrosyl chlorideby yrneansum of oxygen Ato form a gas mixturefcontaining nitrogen peroxide, chlorine and unreacted oxygen, ini troducing nitric oxide into said gas mixture atja temperature at which thef'nitricy oxide reacts i preferentially Withv the free oxygen. instead of With the free chlorine therein', reacting" the nitrogen peroxide in the resulting gas with an aqueous liquid and a portion only of said chlorine.' at .a

temperature at which the nitrogen peroxide is. absorbed by said aqueous 'liquidandreact's -With no Water contained therein to form nitric acidand nitricoxide and this nitric oxide reactswiththe chlorine to form nitrosyl chloride,separating the remaining unreactedchlorine and the nitrosyl.-`

chloride formed by reaction -of lchlorine and, nitric oxide from kthe nitric acid, recycling fthe.

thus separated nitrosyl chloride inthe aforesaid f from said system excess chlorine liberated yby .70".

the aforesaid oxidation of nitrosyl chloride;

HERMAN A. nEEKHUvIsiJg; 

